Photographic element comprising a hydroxy substituted aliphatic carboxylic acid aryl hydrazide

ABSTRACT

HYDROXY SUBSTITUTED ALIPHATIC CARBOXYLIC ACID ARYL HYDRAZIDES ARE EMPLOYED AS DEVELOPING AGENTS FOR EXPOSED ELECTROMAGNETIC ENERGY SENSITIVE SILVER SALTS. THE DEVELOPING AGENTS CAN BE EMPLOYED IN A DEVELOPER SOLUTIONS, IN SILVER SALT SALTS PROCESSING SOLUTIONS, AS INCORPORATED DEVELOPING AGENTS, AS A DEVELOPING AGENT IN DIFFUSION TRANSFER PROCESSES, AND AS THE REDUCING AGENT IN HEAT PROCESSING TECHNIQUES.

3,782,949 PHOTOGRAPHIC ELEMENT COMPRISING A HYDROXY SUBSTITUTEDALIPHATIC CAR- BOXYLIC ACID ARYL HYDRAZIDE Ismael Adolfo Olivares,Frederic Roland Bean, and Grant Milford Haist, Rochester, N.Y.,assignors to Eastman Kodak Company, Rochester, N.Y. No Drawing. FiledMar. 11, 1971, Ser. No. 123,450 Int. Cl. G03c 1/48, 1/06 U.S. Cl. 96-76R 8 Claims ABSTRACT OF THE DISCLOSURE Hydroxy substituted aliphaticcarboxylic acid aryl hydrazides are employed as developing agents forexposed electromagnetic energy sensitive silver salts. The developingagents can be employed in developer solutions, in silver salt processingsolutions, as incorporated developing agents, as a developing agent indiffusion transfer processes, and as the reducing agent in heatprocessing techniques.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to photographic compositions and especially to novel developercompositions exhibiting improved photographic properties. The inventionespecially relates to photographic developer solutions, processingsolutions, photographic elements and photographic emulsions containing anovel developing agent.

Description of the prior art Hydrazines and hydrazine derivatives havebeen employed in photographic emulsions or developers for many purposes.Mees, The Theory of the Photographic Process, 3rd edition, 1966, page281 discloses that few developing agents of importance have been foundamong the hydrazines and/or their derivatives.

The use of a hydrazide in a developing solution and/ or silver halideemulsion is particularly known, however, the compounds are employed assupplemental developers or in a non-developing function, but not asprincipal developing agents. Trivelli et al., U.S. Pat. 2,419,975 issuedMay 6, 1947, for example, describes a method of improving thesensitivity of a silver halide photographic layer by incorporatingtherein a semicarbazide. Honig et al. U.S. Pat. 3,386,831 issued June 4,1968, describes method of stabilizing photographic silver halideemulsions with acyl phenyl hydrazides. Whitmore U.S. Pat. 3,227,552issued Ian. 4, 1966, discovered that a wide variety of hydrazones andhydrazides can be employed as supplemental developing agents in theprocess of preparing photographic direct positive color images. Thedevelopers of this invention are disclosed in Mijovic et al. BritishPat. 1,157,617 as intermediates for the preparation ofl-arylpyrazolid-Zi-ones. The pyrazolid-3-ones are employed asphotographic silver halide developing agents.

Although some hydrazines are interesting, from a historical andtheoretical point of view, as developing agents hydrazines and theirderivatives have been found not to be generally useful.

There is a constant search for compounds which can develop not onlyexposed photographic silver halides, but additionally other photographicsilver salts to visible images. The developing agents should bereasonably fast and should produce images evidencing strong imagediscrimination with little propensity for staining.

It is apparent, in the art, that there is a need to further improve thespeed, particularly for photographic elements to be processed in therapid machine processing systems,

, United. States Patent 3,782,949 Patented Jan. 1, 1974 and to improvethe sensitometric properties of photographic developers.

It is, furthermore, desirable to find developing agents that canadvantageously be employed in a variety of photographic products, forexample, in photographic developer and processing solutions, asincorporated developers in photographic emulsions, in photographicproducts that may be processed according to the so-called dry processing techniques, in photographic diffusion transfer products, etc.

Developing agents having such universal applications are highly unusual.A developing agent, for example, which is desirably employed in adeveloper solution can be useless as an incorporated developing agent,i.e. one incorporated in a photographic emulsion, since the developingagent may not be stable in the emulsion. A developing agent, asincorporated, may cause spontaneous reduction (fogging) or may be lostby oxidation. A developing agent which is incorporated in a photographicelement adapted for wet processing can be generally undesirable forincorporation in a photographic element adapted for dry processing sincedeveloping agents have a tendency to induce staining unless washed outfrom the elements upon processing.

SUMMARY OF THE INVENTION In accordance with this invention photographicsilver salt developing agents are provided which are hydroxy substitutedaliphatic carboxylic acid aryl hydrazides. The developing activity ofthese hydrazides is unobvious and unexpected since similar hydrazidessuch as those of the prior art or aliphatic carboxylic acid arylhydrazide not within the scope of this invention do not manifest anysubstantial developing activity.

It is, therefore, an object of this invention to provide novelphotographic silver salt developing agents capable of providingincreased speeds and strong image discrimination.

A further object of this invention is to provide photographic silversalt developer or processing compositions which provide desiredsensitometric properties and developing action without objectionablestain.

Another object is to provide improved photographic elements and/oremulsions having a developing agent incorporated therein.

Another object of this invention is to provide developing agents whichevidence low staining propensity and therefore need not be washed out ofthe emulsion followmg processing.

It is still a further object of the invention to provide improvedphotographic products, elements, developer compositions and developingprocesses employed in diffusion transfer systems. i

It is yet another object of this invention to provide improvedphotographic products, elements, developer compositions and developingprocesses employed in the socalled dry processing photographic systems.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the presentinvention, novel developing agents are provided which are hydroxysubstituted aliphatic carboxylic acid aryl hydrazides. Suitablehydrazides which can be used in the practice of this invention can berepresented by the general structural formula:

RiNH-NH-d-Ri wherein R is an aryl group including substituted arylgroups are exemplified by phenyl, naphthyl, alkaryl, such as, tolyl,xylyl, mesityl, ethylphenyl, propylphenyl, halide substituted phenylsuch as bromophenyl, dichlorophenyl, carboxyphenyl and the like; and Ris an aliphatic grouping having substituted thereon at least one hydroxygroup. Aliphatic grouping should be understood to include acyclichydrocarbyls having substituted thereon an alicyclic group. In apreferred embodiment of this invention, R can have from 1 to about 6carbons and R, can have from 1 to about 10 carbon atoms.

In another preferred aspect of this invention the hydrazides can berepresented by the general structural formula:

ORa

(II) Rr-NH-NH-C--Ra wherein R is an aryl grouping as described supra andR R and R each alone can be hydrogen, methylol, a lower alkyl such asmethyl, ethyl, propyl, and the like, or R and R form a saturated ringsystem, with the condition that at least one of R R and R is methylol.

Illustrative examples of hydrazides which may be employed according tothe invention are:

The novel developing agents of this invention are readily prepared bymethods well known in the art. The developing agents, for example, canbe prepared by The Method of Donovan, U.S. 2,912,461.

A significant feature and advantage of the developing agents disclosedherein is their substantially low propensity for staining, hence thedeveloping agents need not be washed from a silver salt emulsionfollowing processing. This feature is particularly advantageous anddesirable in rapid machine processing and in photographic elementsadapted for dry processing.

Another significant feature and further advantage of the hydrazides istheir substantial stability when incorpo rated in a photographicelement. The hydrazides neither significantly cause or inducespontaneous reduction, nor are the developing agents lost by oxidation;hence the shelf life of a photographic product is substantiallyextended.

A still further significant feature of the developing agents is theirimproved solubility over many hydrazines and hydrazides of the priorart.

As previously indicated, the novel developing agents of this inventioncan be suitably utilized in any of a variety of locations with respectto the photographic system. They can be employed in photographicprocessing and/or developing solutions, for example, in an aqueousalkaline developer composition. They can be incorporated into a layer ofa photographic element such as a silver halide emulsion layer, anovercoat layer or an interlayer of a photographic element. They can beutilized in a developer composition intended for use in a diffusiontransfer process or they can be utilized in one or more layers of aphotographic element employed in a difiusion transfer process. Diffusiontransfer processes and photographic elements in which the developingagents are useful as described, for example, in U.S. Pats. 2,352,014 ofRott 4 i, issued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951;and 3,337,342 of Green issued Aug. 22, 1967. The developing agents ofthis invention can also be employed in so-called high-speed diffusiontransfer processes as described, for example, in U.S. Pat. 3,326,683 ofLand et al. issued June 20, 1967; or in other types of diffusiontransfer processes such as those described in U.S. Pats. 2,857,274 ofLand et al., issued Oct. 21, 1958; 3,020,155 of Yackel et al., issuedFeb. 6, 1962; 2,584,030 of Land issued Jan. 29, 1952; and 2,923,623 ofLand issued Feb. 2, 1960. These patents describe typical photographicproducts suitable for diffusion transfer systems comprising acombination of (a) a photosensitive element which cornprises a supporthaving thereon at least one photosensltlve silver salt emulsion layer(b) an image-receiving layer, and (c) a rupturable container containingan alkaline processing composition comprising a silver halide developingagent, and typically a silver halide solvent. The novel developingagents of this invention can be utilized in combination withphotosensitive elements which are adapted for processing by theso-called dry photography (heat) development methods. No liquids, vaporsor other processing aids need be employed in order to obtain a highimage density or desirable image tone in the photosensitive elementhaving incorporated therein the novel developers of this invention. Heatdevelopment processes are described, for example, in U.S. Pat. 3,457,075of Morgan et a1. issued July 22, 1969 and 3,152,903 of Sheppard et al.issued Oct. 13, 1964. Other material which can be heat processed aredescribed in British Pats. 1,131,- 108, issued Oct. 23, 1968, 1,161,777,issued Aug. 20, 1969, and 930,572, issued July 3, 1963, U.S. Pats.3,301,678 of Humphlett et al., issued Jan. 31, 1967, 3,531,285 of Haistet al., issued Sept. 29, 1970, 3,392,020 of Yutzy, issued July 9, 1968,and 3,152,904 of Sorensen et al., issued Oct. 13, 1964, and GermanAusligeschrift 1,003,- 578, issued Feb. 28, 1957.

The developing agents employed in the practice of this invention can beemployed for developing an image in a variety of photographic emulsions.The silver halide emulsions employed can comprise silver chloride,silver bromide, silver bromoiodide, silver chlorobromoiodide or mixturesthereof. The emulsions may be coarse or fine grain and can be preparedby any of the well-known procedures, e.g., single jet emulsions, doublejet emulsions, such as Lippmann emulsions, ammoniacal emulsions,thiocyanate or thioether ripened emulsions such as those described inNietz et al. U.S. Pat. 2,222,264 issued Nov. 4, 1940; Illingsworth U.S.Pat. 3,320,069 issued May 15, 1967; and McBride U.S. Pat. 3,271,157issued Sept. 6, 1966. Surface image emulsions may be used or internalimage emulsions such as those described in Davey et al. U.S. Pat.2,592,250 issued Apr. 8, 1952; Porter et al. U.S. Pat. 3,206,313 issuedSept. 14, 1965; Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; andBacon et al. U.S. Pat. 3,447,927 issued June 3, 1969. If desired,mixtures of surface and internal image emulsions may be used asdescribed in Luckey et al. U.S. Pat. 2,996,382 issued Apr. 15, 1961.Negative type emulsions may be used or direct positive emulsions such asthose described in Leermakers U.S. Pat. 2,184,013 issued Dec. 19, 1939;Kendall et al. U.S. Pat. 2,541,472 issued .Feb. 13, 1951; Berriman U.S.Pat. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Pat. 723,019;Illingsworth et al. French Pat. 1,520,821; Ives U.S. Pat. 2,563,785issued Aug. 7, 1951; Knott et al. U.S. Pat. 2,456,953 issued Dec. 21,1968; and Land U.S. Pat. 2,861,885 issued Nov. 25, 1958. The emulsionsmay be regular grain emulsions such as the type described in Klein andMoisar, J. Phot. Sci., vol. 12, No. 5, September/October 1964, p.242-251.

The developing agents or reducing agents, as commonly referred to in theart of dry photography, whi h have unexpectedly found to be suitable asa primary d p g Component in accordance with this invention can beemployed in combination with any silver salt developing agent. Suitablesilver halide developing agents which can be employed with thedeveloping agents of the invention include, for example,polyhydroxybenzenes, such as hydroquinone developing agents, e.g.,hydroquinone, alkyl substituted hydroquinones such ast-butyl-hydroquinone, methylhydroquinone and 2,5-dimethyl hydroquinone;catechols and pyrogallol; halogen substituted hydroquinones such aschlorohydroquinone or dichlorohydroquinone; alkoxy substitutedhydroquinones such as methoxyhydroquinone or ethoxyhydroquinone;aminophenol developing agents, such as 2,4-diaminophenols, e.g.,2,4-diamino-6-methylphenol, and methylaminophenols; ascorbic acid,ascorbic acid ketals, such as those described in Green U.S. Pat.3,337,342 issued Aug. 22, 1967; hydroxylamines such asN,N-di(2-ethoxyethyl)hydroxyamine; 3-pyrazolidone developing agents suchas 1-phenyl-3-pyrazolidone, including those described in British Pat.930,572; and acyl derivatives of p-aminophe- 1101 such as described inBritish Pat. 1,045,303; hydroxytetronic acid and hydroxytetronimidedeveloping agents; reductone developing agents such asanhydrodihydropyrrolidino hexose reductone and the like.

In accordance with another embodiment of the invention, photographicdeveloper compositions are provided comprising the silver saltdeveloping agents described herein.

The photographic developer compositions can include ingredients commonlyemployed for processing photographic elements in addition to thedeveloping agent, e.g., stabilizer compositions monobaths, activatorcompositions, hardener compositions and the like.

The photographic developer compositions according to the invention cancontain a silver halide solvent. A variety of silver halide solvents aresuitable, such as alkali metal and ammonium thiocyanates, e.g., sodiumand potassium thiocyanate and ammonium thiocyanate, alkali metalthiosulfates, such as sodium thiosulfate and potassium thiosulfate,thiourea compounds, and the like.

The developing agents of the invention can be employed in processingcompositions in any form suitable for developing an exposed photographicelement. For example, at least one developing agent of this inventioncan be employed alone or with one or more auxiliary developing agentsdescribed herein. The developing agents can be provided as an aqueoussilver halide developer solution or liquid concentrate; as a componentof a solid particulate composition suitable for dissolving in a solventsuch as an aqueous-solvent; as a viscous composition containing variousthickening agents; as a packaged component of a kit for mixing withvarious processing agents or as a component of a fusible solid such assolid containing a homogeneous mixture of an alkylene oxide polymer anda developing agent of the invention said fusible solid melting aboveabout room temperature, and the like.

A further aspect of the invention is a photographic process fordeveloping exposed silver salt layers of a photographic element, saidprocess comprising contacting the silver salt layer with the developingagents of this invention in the presence of an alkaline developmentactivator. In accordance with this aspect, the invention can comprise aprocess of developing the exposed silver salts in a photographic silversalt layer by contacting the silver salt layer with a processingcomposition containing a silver halide solvent andthe novel silverhalide developing agent. i

The process according to this aspect can also employ other silver halidedeveloping agent, as described herein, as an auxiliary developing agent.The auxiliary developing agents can be located in a layer of aphotographic element to be processed and/or in the silver halideprocessing composition. Developing action is effected upon contact ofthe developing components of the invention with a suitable activator.

Any alkaline developer activator can be employed to activate thedeveloping agents of the invention in nondry processing photographicprocesses so long as the activators provide the desired pH. Theseinclude those commonly employed in the photographic art as developmentactivators, such as inorganic alkali, e.g., alkali metal hydroxideincluding sodium hydroxide, potassium hydroxide and lithium hydroxide,alkali metal carbonate, such as sodium carbonate, sodium bicarbonate,fuming ammonia, and the like as Well as organic alkali such as organicamines and aminoalkanols, e.g., ethanol amines and aminodiethanolamineor morpholine. The concentration of development activator can varydepending on the various components of the system, the photographicemulsion employed, the desired image, and the like. A concentration isusually employed which provides a pH of at least about 8, typically fromabout 10 to about 14, and preferably about 11 to about 14.

In another embodiment of the invention, photosensitive elements areprovided, said elements comprising a support, at least one silver saltlayer and incorporated in said element, a photographic silver saltdeveloping agent of this invention. The developing agent can be employedin a photographic silver salt emulsion layer, an overcoat layer, a layerunder the emulsion layer, or virtually any of the layers contiguous tothe silver salt to be developed.

The developing agents of the invention can be employed in photographicelements designed for processing in stabilization type processing. Forexample, they can be incorporated in one or more layers of aphotographic element which is exposed, activated by contact withalkaline activator, and then contacted with a thiocyanate or thiosulfatesolution, such as an ammonium thiocyanate, or they can be incorporatedin the alkaline activator. Such processes are described, for example, inU.S. Pat. 3,326,- 864 of Nishio issued June 20, 1967; British Pat.1,004,302; French Pat. 1,516,556 of Fassbender; and in an article by H.D. Russell, E. C. Yackel and I. S. Bruce in the PSA Journal, August1950, pp. 59-62, entitled Stabilization Processing of Films and Papers.

The developing agents of this invention as described herein can be usedin layers of photographic elements or processing solutions intended foruse in monobath processing such as described in U.S. Pat. 2,875,048 of'Haist et al. issued Feb. 24, 1959, and British Pat. 1,063,844 ofBeavers et al. issued Mar. 30, 1967; and in web-type processing, such asdescribed in U.S. Pat. 3,179,517 of Tregillus et al. issued Apr. 20,1965.

The developing agents of this invention can be employed in aphotographic silver salt emulsion designed for diffusion transferprocessing and/or in a developer composition designed for developing andstabilizing the element. A typical developer composition is disclosed inU.S. Pat. 3,120,795 of Land et al. issued Feb. 11, 1964.

Hence, in accordance with an aspect of the invention there isaccordingly provided in combination (a) a photographic elementcomprising a photographic silver salt layer, (b) a viscous processingcomposition, within a releasing means, e.g., a rupturable container,comprising:

(i) a silver halide solvent,

(ii) an alkaline development activator,

(iii) optionally, a 3-pyrazolidone developing agent, adiaminophenoldeveloping agent or other auxiliary developing agent described herein,and

(iv) the novel developing agents of this invention, and

(c) an image receiving layer comprising development nuclei, especiallypalladium development nuclei, dispersed in a polymeric binder.

, Albeit the developing agents are generally located in a releasingmeans, the developing agents can be suitably employed in a variety oflocations with regard to a diffusion transfer system. The noveldeveloping agents can be provided in the silver salt layer or emulsion,in a layer near to the silver salt layer, in the image receiving layercontaining silver precipitating nuclei or development nuclei as well asin the rupturable container.

In accordance with a typical difiusion transfer process a photographicelement is exposed imagewise, the exposed silver halide is developed ata pH above 8, typically above 10 and preferably at a pH of about 12 toabout 14, in the presence of the novel developers, the unexposed silversalts in the photosensitive silver salt layer is contacted with a silverhalide solvent to form an imagewise distribution of a silver complex inthe unexposed areas of said photographic silver salt layer; and at leastpart of the silver complex is transferred to an image receiver layercontiguous to the photosensitive layer, said receiver layer containingdevelopment nuclei, thereby forming a visible image on said receiverlayer.

Processing conditions, time of development, and the like can varydepending on the desired image, the particular components of thedescribed element, processing composition, and image receiver. Typicallyprocessing is carried out under normal atmospheric conditions and iscompleted within about 60 seconds, e.g., within about 10 seconds.

Usually the silver halide solvent will be sodium thiosulfate; however,various organic silver halide complexing agents such as those describedby Haist et al., Phot. Sci. Eng, 5, 198 (1961) and in Kodak French Pat.1,312,687 issued Nov. 12, 1962, and Belgian Pat. 606,559 of Ulrich etal. issued July 26, 1960, and similar agents can also be used.

The light-sensitive element, receiving element or processing compositioncan also contain toning agents such as, for example, polyvalentinorganic salts of the type described in U.S. Pat. 2,698,236 of Landissued Dec. 28, 1954, silica as described in U.S. Pat. 2,698,237 of Landissued Dec. 28, 1954, and heterocyclic mercaptans such as the mercaptoazoles, e.g., mercapto diazoles, mercapto triazoles and mercaptotetrazoles.

Typically, the developing agent is provided in a viscous liquidphotographic developer composition comprising (a) a silver halidesolvent, and (b) the saliver halide developing agent of the invention.The viscous liquid photographic developer composition can also contain asecond silver halide developing agent, as described herein, especially a3-pyrazolidone silver halide developing agent.

A viscous liquid photographic developer composition can comprise aviscous monobath. Suitable viscous monobaths are described, for example,in the Monobath Manual, Morgan & Morgan, New York, by Grant M. Haist(1966).

Typically, a suitable developer composition according to the inventioncan comprise a viscous developer containing:

(a) a silver halide solvent, such as sodium thiosulfate, (b) adiaminophenol auxiliary developing agent, such as 6-methoxy 2,4diaminophenol or 6-ethyl-2,4-diaminophenol or a 3-pyrazolidone auxiliarydeveloping agent such as 1-phenyl-3-pyrazolidone or1-phenyl-4,4-dimethyl-3-pyrazolidone,

(c) the developing agent of the invention,

(d) an alkaline development activator, and

(e) a thickening agent, such as a cellulose derivative, e.g.,hydroxyethyl cellulose and/or carboxymethyl cellulose.

in the photographic process generally referred to as dry photography.The elements employed in dry photography are photosensitive, i.e., alatent image is formed image- Wise in the exposed areas of a silver saltlayer, and thermosensitive, i.e., substantially permanent visible imagesof photographic sharpness and high visual contrast can be produced oftenwithin seconds through the mere application of heat. The dryphoto-graphic elements are developed by heating to within a temperaturerange of from about C. to about 250 C. 7

Typically a dry photographic element comprises a support having thereonan oxidation-reduction image forming combination said combinationcomprising a silver salt, preferably an organic silver salt, and areducing agent, and a catalyst for the oxidation-reduction image formingcombination. I

In accordance with an aspect of the invention the hydrazides describedherein can be employed as a reducing agent in the dry photographicelement.

Other reducing agents as described herein can be mployed in combinationwith the hydrazides of this invention, and include, for example, theprior art silver halide developing agents and/or substituted phenols andnaphthols as described in deMauriac, U.S. Ser. No. 33,964 filed May 1,1970 now U.S. Pat. 3,672,904.

As the oxidizing agent, of the oxidizing-reduction image formingcombination a silver salt of an organic acid is preferably employed. Thesilver salt of the organic acid should be resistant to darkening underillumination to prevent undesired deterioration of a developed image. Anespecially suitable class of silver salts of organic acids is the waterinsoluble silver salts of long-chain fatty acids which are stable tolight. Typically, the silver salts include silver behenate, silverstearate, silver oleate, silver laurate, silver hydroxystearate, silvercaprate, silver myristate, and silver palmitate. Other suitableoxidizing agents are silver benzoate, silver phthalazinone, silverbenzotriazole, silver saccharin, silver4'-n-octadecyloxydiphenyl-4-carboxylic acid, silver ortho-aminobenzoate,silver acetamidobenzoate, silver furoate, silver camphorate, silverpphenylbenzoate, silver phenyl acetate, silver salicylate, silverbutyrate, silver terephthalate, silver phthalate, silver acetate, andsilver acid phthalate. Nonsilver salts can be employed as oxidizingagents, such as zinc oxide, gold stearate, mercuric behen-ate, auricbehen'ate land the like; however, silver salts are generally preferred.

Typically, a photosensitive silver salt is present in dry photographicelements in minor or catalytic amounts and in catalytic proximity to theoxidation image-forming component of the image-forming combination. Asuitable concentration range of the catalyst is generally from about0.01 to about 0.50 mole of photosensitive silver salt per mole ofoxidizing agent. Suitable silver salts include photosensitive silverhalides, e.g., silver chloride, silver bromide, silver bromoiodide,silver chlorobromoiodide, or mixtures thereof. The photosensitive silverhalide can be coarse or fine-grain, very fine-grain emulsions beingespecially useful. The emulsion containing the photosensitive silverhalide can be prepared by any of the well-known procedures in thephotographic art, such as single-jet emulsions, double-jet emulsions,such as Lippmann emulsions, ammoniacal emulsions, thiocyanate orthioether ripened emulsions, such as those described in U.S. Pat.2,222,264 of Nietz et al. issued Nov. 14, 1940; U.S. Pat. 3,320,069 ofIllingsworth issued May 15, 19,67, and U.S. Pat. 3,271,157 of McBrideissued Sept 6, 1966. Surface image silver halide emulsions can be used.If desired, mixtures of surface and internal image silver halideemulsions can be used as described in U.S. Pat. 2,996,382 of Luckey etal. issued Apr. 15, 1961. Negative type emulsions can be used. Thesilver halide emulsion can be a regular grain emulsion such as describedin Klein and Moisar, Journal of Photographic Science, volume 12, No. 5,September- October (1964), pages 242-251.

The dry photographic elements preferably contain an activator-toningagent. Suitable activator-toning agents which can be employed includecyclic imides such as:

Phthalimide, N-hydroxyphthalimide, N-potassium phthalimide, N-mercuryphthalimide, Succinimide, and t N-hydroxysuccinimide.

Other activator-toning agents can be employed in combination with or inplace of the cyclic imides. Such other activator-toning agents aregenerally heterocyclic compounds containing at least two hetero atoms inthe heterocyclic ring at least one being nitrogen. Illustrativecompounds include phthalazinone, phthalic anhydride, 2-acetylphthalazinone and Z-phthalylphthalazinone. Grant, U.S. Pat.3,080,254 issued Mar. 5, 1963, and Workman U.S. Pat. 3,446,648 issuedMay 27, 1969, describe suitable activator-toning agents.

Activator-toning agents are suitably employed at a concentration ofabout 0.10 mole to about 1.05 moles per mole of oxidizing agent,however, lower and higher concentrations can be employed.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for illustrating this invention.

EXAMPLE 1 Strips of a fine grain silver bromoiodide emulsion are exposedbehind a step wedge to produce a sensitometric exposure and developed at20 C. for a series of times in the following developer composition:

Mole

Developing agent 0.02 Sodium sulfite 0.2 Trisodium phosphate 0.2 Waterto 1 liter.

The pH is adjusted to 11.5 with acetic acid. The developing agentsemployed are:

(1) Phenylhydrazine (2) Formyl-B-phenylhydrazide 3 2,2bis (hydroxymethylpropionyl-B-phenylhydrazide (4)2,2,2-tris(hydroxymethyl)acetyl-B-phenylhydrazide (5)3-hydroxypivalyl-/3-phenylhydrazide The activity of the developer ismeasured in terms of the time required to obtain a normal degree ofdevelopment, namely, a density of 1.5 on the fourth step of thesensitometric strip. The corresponding density of the unexposed area(fog) is also read. The results are entered in Table I.

TAB LE I Developing Time Image Fog agent (min.) density density EXAMPLE2 Twenty mg. samples of the developing agents described below are placedin two sets of ml. beakers. To one set is added 1 ml. each of a 4%sodium hydroxide solution; to the other set is added 1 ml. each of asolution comprising 4% sodium hydroxide and 6% sodium sulfite. Eachsolution is absorbed into a 1 /2 x 2 inch strips of chromatographicpaper. The strips are placed in a museum jar over water for 24 hours atroom temperature. The strips are dried and the densities read to neutraltransmitted light on a densitometer. The density of an untreated paperbase is subtracted. to give net stain density. The results aresummarized in Table II.

The low staining propensity of the developers of this invention isevident in the low density shown by this test.

TAB LE II Density to transmitted light Developing agent No sulfite Withsulfite Hydroquinone.-- 1. 0. 34 1 0. 08 0.02 2 0. 24 0. 08 3"--- 0.090.03 2, 4-diarninophenol... 3. 82 2. 75

Nora-1 =2, 2-bis (hydroxymethybpropilom l-B-pheny 1h drazide; 2 2, 2,Z-tris (hydroxymethyl) acetyl-fi-phenylh'g, drazide; 3 =3-hydroxypivalyl-B-phenylhy drazide.

EXAMPLE 3.USE IN DRY PROCESSING SYSTEMS A dispersion is prepared bymixing the following components:

G. Silver behenate 23.3 Behenic acid 26.0 Polyvinyl butyral 1.25 Sodiumbromide 1.31

Acetone-toluene 1:1 parts by volume), 500 ml.

The mixture is ball milled for 18 hours. Phthalazinone is thenincorporated as an activator-toner at a weight concentration of about /2that of the silver behenate. Hydrazides of the invention areincorporated in the mixture from alcohol-acetone solution. Theconcentration in weight is approximately the weight of the silverbehenate. The emulsions are exposed to light behind a graphic testobject and processed by heating to C. Strong black images are obtainedas shown in the Table III.

Similar results are also obtained when phthalimide is employed as theactivator-toner.

In the absence of an activator-toner, satisfactory images were obtainedalthough the tone was less neutral.

EXAMPLE 4.INCORPORATION IN EMULSION Compound 3 of Example 1 is added ata concentration of 4.76 grams per gram of silver to a gelatin silverchloride emulsion. In a similar preparation 4.76 grams of 3-S-thi-uronium-l-methyl propanesulfonate is also added. The emulsions areprocessed by immersion in a sodium hydroxide solution. High density andlow stain levels are obtained in the sodium hydroxide activators. It isnot necessary to wash these strips to prevent stain formation ascontrasted to the hydroquinone control which shows strong stainformation unless washed vigorously. The emulsions subjected toincubation for 14 days at F. and 35% relative humidity showed no loss inactivity or a propensity for increase in fogging.

EXAMPLE 5 Developer formulations are prepared in the same manner as inExample 1, substituting the developers as summarized in Table III forthose employed in Example 1.

Strips of a fine grain silver bromoiodide emulsion are processed in thesame manner as in Example 1. The results are summanzed in Table IV.

The concentrations of the developing agents employed in accordance withthe invention can vary over wide ranges depending upon the particularphotographic and physical variables of the photographic system. Typicalof the variable which effect the concentration of the developing agentsare the location in the photographic element, the developer composition,the desired image, etc. Suitable concentrations are also dependent onprocessing conditions, addenda present in the photographic element to beprocessed and/or in the processing compositions. Suitable optimumconcentrations can be easily determined by those skilled in the artthrough routine experimentation. Typically, when a developing agentdescribed herein is incorporated in a photographic element, theconcentration can vary from about 0.25 to about moles of developingagent per mole of silver present in the photographic element. A morepreferred range is from about 1 to about 10 moles per mole of silverpresent. When a developing agent as described is employed in acomposition for processing of a photographic element, the totalconcentration of developing agents can vary from about 1 to about 100g./l. and preferably from about 2 to 20 ./l. g As employed in a dryphotographic element the hydrazides of this invention can be present inan amount of from about 0.05 to about 3 moles per mole of oxidant andreferably from about 0.25 to 2.0 moles per mole of oxidant.

The particular time required for developing the photographic elementsdescribed herein can vary over a wide range such as from about a fewseconds up to an hour or more, depending on the photographic elementutilized, the desired image, the various addenda employed, etc. Theoptimum developing time can be obtained by routine experimentation.

Silver precipitating or development nuclei or agents which can beemployed in diffusion transfer systems as described can be physicaldevelopment nuclei or chemical precipitants including: (a) heavy metalsin colloidal form and salts of these metals, (b) salts of amines whichform silver salts and/or (c) non-difiusion polymeric materials withfunctional groups capable of combining with the silver amine. Suitablesilver precipitating agents and/or nuclei within the above classesinclude metal sulfides, selenides, polysulfides, polyselenides, thioureaderivatives, stannous halides, silver, gold, platinum, palladium, andmercury, colloidal silver and similar agents disclosed, for example, inU.S. Pat. 3,020,155 of Yackel et al. issued Feb. 6, 1962. A wide rangeof concentrations of the silver precipitating agents and nuclei can beemployed. The concentration of silver precipitant or nuclei in thereceiving layer or receiving sheet must be at least sufficient to ensurea positive and sufiicient removal of undeveloped silver salt from thelight-sensitive layer to be processed. Usually, the concentration ofdeveloping agent described is about 3 to about 320 milligrams per squarefoot of the layer containing the precipitants or nuclei.

The silver halide emulsions employed with the developers of thisinvention may be unwashed or washed to remove soluble salts. In thelatter case the soluble salts may be removed by chill-setting andleaching or the emulsion may be coagulation washed, e.g. by theprocedures described in Hewitson et al. U.S. Pat. 2,618,556 issued Nov.18, 1952; Yutzy et al. U.S. Pat. 2,614,928 issued Oct. 21, 1952; YackelU.S. Pat. 2,565,418 issued Aug. 21, 1951; Hart et al. U.S. Pat.3,241,969 issued Mar. 22, 1966; and Waller et al. U.S. Pat. 2,489,341issued Nov. 29, 1949.

The emulsions employed with the developing agents of this invention maybe sensitized with chemical sensitizers, such as with reducing agents;sulfur, selenium or tellurium compounds; gold platinum or palladiumcompounds; or combinations of these. Suitable procedures are describedin Sheppard et al. U.S. Pat. 1,623,499 issued Apr. 5, 1927; Waller etal. U.S. Pat. 2,399,083 issued Apr. 23, 1946; McVeigh U.S. Pat.3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat. 3,297,446 issued Jan.10, 1967.

Development modifiers can be employed in combination with the silverhalide emulsions as described in this invention. Typical developmentmodifiers include polyalkylene glycols, cationic surface active agentsand thiocthers or combinations of these as described in Piper U.S. Pat.2,886,437 issued May 12, 1959; Dann et al. U.S. Pat. 3,046,134 issuedJuly 24, 1961; Carroll et al. U.S. Pat. 2,944,900 issued July 12, 1960;and Goffe U.S. Pat. 3,294,540 issued Dec. 27, 1966.

The silver halide emulsions used in the practice of this invention canbe protected against the production of fog and can be stabilized againstloss of sensitvity during keeping. Suitable antifoggants and stabilizerseach used alone or in combination include thiazolium salts described inBrooker et al. U.S. Pat. 2,131,038 issued Sept. 27, 1938, and Allen etal. U.S. Pat. 2,694,716 issued Nov. 16, 1954; the azaindenes describedin Piper U.S. Pat. 2,886,437 issued May 12, 1959, and Heimbach et al.U.S. Pat. 2,444,605 issued July 6, 1948; the mercury salts as describedin Allen et al. U.S. Pat. 2,728,663 issued Dec. 27, 1955; the urazolesdescribed in Anderson et al. U.S. Pat. 3,287,135 issued Nov. 22, 1966;the sulfocatechols described in Kennard et al. U.S. Pat. 3,236,652issued Feb. 22, 1966; the oximes described in Carroll et al. BritishPat. 623,448; nitron; nitroindazoles; the mercaptotetrazoles describedin Kendall et al. U.S. Pat. 2,403,927 issued July 16, 1946, Kennard etal. U.S. Pat. 3,266,897 issued Aug. 16, 1968, and Luckey et al. U.S.Pat. 3,397,987 issued Aug. 20, 1968; the polyvalent metal saltsdescribed in Jones U.S. Pat. 2,839,405 issued July 17, 1958; thethiuronium salts described in Herz et al. U.S. Pat. 3,200,- 839 issuedNov. 30, 1965; the palladium, platinum and gold salts described inTrivelli et al. U.S. Pat. 2,566,263 issued Aug. 28, 1951, and Yutzy etal. U.S. Pat. 2,597,915 issued May 27, 1952.

The photographic and other hardenable layers used in the practice ofthis invention can be hardened by various organic or inorganichardeners, alone or in combination, such as the aldehydes, and blockedaldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonateesters sulfonyl halides and vinyl sulfonyl ethers, active halogencompounds, epoxy compounds, aziridines, active olefins, isocyanates,carboiimides, mixed function hardeners and polymeric hardeners such asoxidized polysaccharides like dialdehyde starch and oxyguargum and thelike.

The photographic emulsions and elements described in the practice ofthis invention can contain various colloids alone or in combination asvehicles, binding agent and various layers. Suitable hydrophilicmaterials include both naturally-occurring substances such as proteins,for example, gelatin, gelatin derivatives, cellulose derivatives,polysaccharides such as dextran, gum arabic and the like; and syntheticpolymeric substances such as water soluble polyvinyl compounds likepoly(vinylpyrrolidone), acrylamide polymers and the like.

The described photographic emulsion layers and other layers of aphotographic element employed in the practice of this invention can alsocontain alone or in combination with hydrophilic, water permeablecolloids, other synthetic polymeric compounds such as dispersed vinylcompounds such as in latex form and particularly those which increasethe dimensional stability of the photographic materials. Suitablesynthetic polymers include those described, for example, in Nottorf U.S.Pat. 3,142,568 issued July 28, 1964; White U.S. Pat. 3,193,386 issuedJuly 6, 1965; Houck et al. U.S. Pat. 3,062,674 issued Nov. 6, 1962;Houck et al. U.S. Pat. 3,220,844 issued Nov. 30, 1965; Ream et al. U.S.Pat. 3,287,289 issued Nov. 22, 1966; and Dykstra U.S. Pat. 3,411,911issued Nov. 19, 1968; particularly eifective are those water-insolublepolymers of alkyl acrylates and methacrylates, acrylc acid, sulfoalkylacrylates or methacrylates those which have cross-linking sites whichfacilitate hardening or curing, those having recurring sulfobetaineunits as described in Dykstra Canadian Pat. 774,054.

The photographic elements and emulsions used with this invention maycontain antistatic or conducting layers, such layers may comprisesoluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers,ionic polymers such as those described in Minsk U.S. Pat. 2,861,056issued Nov. 18, 1958 and Sterman et al. U.S. Pat. 3,206,312 issued Sept.14, 1965, or insoluble inorganic salts such as those described in TrevoyU.S. Pat. 3,428,451 issued Feb. 18, 1969.

The photographic layers and other layers of a photographic elementemployed in the practice of this invention can be coated on a 'widevariety of supports. Typical supports include cellulose nitrate film,cellulose ester film, poly(vinyl acetal) film, polystyrene film,poly(ethylene terephthalate) film, polycarbonate film and related filmsor resinous materials, as well as glass, paper, metal and the like.Typically a flexible support is employed, especially a paper support,which can be partially acetylated or coated with baryta and/ or analpha-olefin polymer, particularly a polymer of an alpha-olefincontaining 2 to carbon atoms such as polyethylene, polypropylene,ethylenebutene copolymers and the like.

The photographic layers employed in the practice of this invention cancontain plasticizers and lubricants such as polyalcohols, e.g., glycerinand diols of the type described in Milton et al. U.S. Pat. 2,960,404issued Nov. 1, 1966; fatty acids or esters such as those described inRobins U.S. Pat. 2,588,765 issued Mar. 11, 1952 and Duane U.S. Pat.3,121,060 issued Feb. 11, 1964; and silicone resins such as thosedescribed in Du Pont British Pat. 955,061.

The photographic elements employed in the practice of this invention maycontain matting agents such as starch, titanium dioxide, zinc oxide,silica, polymeric beads including beads of the type described in Jellyet a1. U.S. Pat. 2,992,101 issued July 11, 1961, and Lynn U.S. Pat.2,701,245 issued Feb. 1, 1955. I

The photographic elements and emulsions used in this invention maycontain brightening agents including stilbenes, triazines, oxazoles andcoumarin brightening agents. Water soluble brightening agents may beused such as those described in Albers et al. German Pat. 972,067 andMcFall et al. U.S. Pat. 2,933,390 issued Apr. 19, 1960, or dispersion ofbrighteners may be used such as those described in Jansen German Pat.1,150,274, Oetiker et al. U.S. Pat. 3,406,070 issued Oct. 15, 1968, andHeidke French Pat. 1,530,244.

Spectral sensitizing dyes can be used conveniently to confer additionalsensitivity to light sensitive silver halide emulsions employed in thepractice of this invention. For instance, additional spectralsensitization can be obtained by treating the emulsion with a solutionof a sensitizing dye in an organic solvent or the dye may be added in 14the form of a dispersion as described in Owens et al. British Pat.1,154,781. For optimum results, the dye may either be added to theemulsion as a final step or at some earlier stage.

Sensitizing dyes useful in sensitizing such emulsions are described, forexample, in Brooker et al. U.S. Pat. 2,526,- 632 issued Oct. 24, 1950;Sprague U.S. Pat. 2,503,776 issued Apr. 11, 1950; Brooker et al. U.S.Pat. 2,493,748 issued 1 an. 10, 1950; and Taber et al. U.S. Pat. 3,384,486 issued May 21, 1968. Spectral sensitizers which can be usedinclude the cyanines, merocyanines, complex (trior tetranuclear)merocyanines, complex (trior tetranuclear) cyanines, holopolar cyanines,styryls, hemicyanines (e.g. enamine hemicyanines), oxonols andhemioxonols.

Dyes of the cyanine classes may contain such basic nuclei as thethiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles,selenazoles and imidazoles. Such nuclei may contain alkyl, alkylene,hydroxyalkyl, sulfo alkyl, carboxyalkyl, aminoalkyl, and enamine groupsand may be fused to carbocyclic or heterocyclic ring systems eitherunsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl,cyano, or alkoxy groups. The dyes may be symmetrical or unsymmetricaland may contain alkyl, phenyl, enamine or heterocyclic substituents onthe methine or polymethine chain.

The merocyanine dyes may contain the basic nuclei mentioned above aswell as acid nuclei such as thiohydantoins, rhodanines,oxazolidenediones, thiazolidenediones, barbituric acids thiazolindiones,and malonitrile. These acid nuclei may be substituted with alkyl,alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl,alkylamino groups, or heterocyclic nuclei. Combinations of these dyesmay be used, if desired. In addition, supersensitizing addenda which donot absorb visible light may be included, for instance, ascorbic acidderivatives, azaindenes, cadmium salts, and organic sulfonic acids asdescribed in McFall et al. U.S. Pat. 2,933,390 issued Apr. 19, 1960, andJones et al. US. Pat. 2,937,089 issued May 17, 1960.

The various layers including the photographic layers, employed in thepractice of this invention can contain light absorbing materials andfilter dyes such as those described in Sawdey U.S. Pat. 3,253,921 issuedMay 31, 1966; Gaspar U.S. Pat. 2,274,782 issued Mar. 3, 1942;Silberstein et al. U.S. Pat. 2,527,583 issued Oct. 31, 1950; and VanCampen U.S. Pat. 2,956,879 issued Oct. 18, 1960. If desired, the dyescan be mordanted, for example, as described in Jones et al. U.S. Pat.3,282,699 issued Nov. 1, 1966.

The photographic layers employed in the practice of this invention maycontain surfactants such as saponin; anionic compoundssuch as the alkylaryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831 issued June17, 1962; amphoteric compounds such as those described in Ben-Ezra U.S.Pat. 3,133,816 issued May 19, 1964; and water soluble adducts ofglycidol and an alkyl phenol such as those described in Olin MathiesonBritish Pat. 1,022,878.

The photographic layers of photographic elements used in the practice ofthis invention may be coated by various coating procedures including dipcoating, air knife coating, curtain coating, or extrusion coating usinghoppers of the type described in Beguin US. Pat. 2,681,294 issued June15, 1954. If desired, two or more layers may be coated simultaneously bythe procedures described in Russell U.S. Pat. 2,761,791 issued Sept. 4,1956, and Wynn British Pat. 837,095. This invention also can be used forsilver halide layers coated by vacuum evaporation as described inBritish Pat. 968,453 and LuValle et al. U.S. Pat. 3,219,451 issued Nov.23, 1965.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

There is claimed:

1. In a photographic element comprising a support having thereon atleast one photosensitive silver halide layer, and a silver halidedeveloping agent, the improvement comprising a hydrazide represented bythe structural formula:

Ri--NHNH Rz wherein R is an aryl group and R is an aliphatic groupcontaining from 1 to about 6 carbon atoms and containing at least 1hydroxy group, as the developing agent.

2. A photographic element of claim 1 wherein said developing agent is2,2-bis(hydroxymethyl)propionyl-,6- phenylhydrazide.

3. A photographic element of claim 1 wherein said developing agent ispresent in said silver halide layer.

4. A photographic element of claim 1 wherein said developing agent is ina layer contiguous to said silver halide layer.

5. A photographic element of cliam 1, said element having contiguousthereto an image receiving layer.

6. In a photographic product comprising (a) a photosensitive element',said element comprising a support having thereon at least onephotographic silver halide layer, (b) a releasing means containing aphotographic processing solution comprising at least one developingagent, and (c) an image receiving layer, the improvement comprisingemploying a hydrazide represented by the formula:

wherein R is an aryl group and R is an aliphatic group containing from 1to about 16 carbon atoms and containing at least 1 hydroxy group as thedeveloping agent.

8. A photographic emulsion as in claim 6 wherein said binder comprises ahydrophilic colloid.

References Cited UNITED STATES PATENTS 2,419,974 5/1947 Stauifer 96-662,419,975 5/ 1947 Trivelli et a1. 96-95 2,563,785 8/1951 Ives 96-952,592,368 4/1952 Yackel 96-95 2,740,717 4/1956 Yutzy et a1. 96-953,227,552 1/1966 Whitmore 96-3 3,447,923 6/1969 Jaeken 96-55 NORMAN G.TORCHIN, Primary Examiner M. F. KELLEY, Assistant Examiner

